Control of insects and acarinae with thiolphosphoric acid esters

ABSTRACT

New thiolphosphoric acid esters, their manufacture and use as pesticides is disclosed. The compounds correspond to the formula   wherein R1 represents methyl or ethyl, R2 represents n-pentyl, sec. pentyl, or methoxyethyl and R3 and R4 each represents methoxy, ethoxy, n-propoxy, isopropoxy or n-hexyloxy, and are effective against insects and representatives of the order Acarina.

United States Patent Beriger Aug. 5, 1975 [54] CONTROL OF INSECTS ANDACARINAE 3,309,371 3/l967 DuBreuil et al. 260/942 X WITH THIOLPHOSPHORICACID ESTERS FOREIGN PATENTS OR APPLICATIONS [7 51 In n r: Ern B rig r,All h il. 1,001.065 8/1965 United Kingdom 260/942 Switzerland [73]Assignee: Ciba-Geigy Corporation, Ardsley, Pri' 7mry '7 D"Go ldbergAsslstant E.\'ammerAllen J Robmson Attorney, Agent, or FirmFrederick H.Rabin [22] Filed: Oct. 25, 1974 21 Appl. No.2 517,977 ABSTRACT RelatedU.S. Application Data [30] Foreign Application Priority Data Apr. 27.l972 Switzerland 6265/72 Mar. 15, l973 Switzerland 3775/73 [52] U.S. Cl.424/212 [51] Int. Cl AOln 9/36 [58] Field of Search 424/212 [56]References Cited UNITED STATES PATENTS 2,713,018 7/1955 Johnson 260/942X New thiolphosphoric acid esters, their manufacture and use aspesticides is disclosed. The compounds correspond to the formula whereinR represents methyl or ethyl, R represents n-pentyl, sec. pentyl, ormethoxyethy] and R and R, each represents methoxy, ethoxy, n-propoxy,isopropoxy or n-hexyloxy, and are effective against insects andrepresentatives of the order Acarina.

9 Claims, No Drawings CONTROL OF INSECTS AND ACARINAE WITHTHIOLPHOSPHORIC ACID ESTERS This is a division of application Ser. No.354,614, filed on Apr. 25, 1973, now US. Pat. No. 3,859,391, issued Jan7, 1975.

The present invention relates to thiolphosphoric acid esters, processesfor their manufacture, and to their use in pest control.

The thiolphosphoric acid esters have the formula wherein R respresentsmethyl or ethyl, R represents n-pentyl, sec. pentyl, or methoxyethyl andR and R each represents methoxy, ethoxy, n-propoxy, isopropoxy orn-hexyloxy.

Preferred compounds on account of their activity are those of theformula I, wherein R represents methyl or ethyl, R representsmethoxyethyl, and R and R represent methoxy, ethoxy or isopropoxy.

Analogous compounds are described as insecticides in German Pat. No.1.164.408, but compared with these, the compounds of the formula Idisplay a surprisingly better activity against insects, in particularagainst eating and sucking insects.

It is possible to manufacture the compounds of the formula I by thefollowing methods described e.g. in US. Pat. No. 2,578,652:

0 IO II HalCHCOR,,-- l 1) R. ,s

(11) CH2COR,

o CH-CORA H H PSH CH-COR, R s (1V) v 3) 11,0 5 s H II PSCHCOR 1 R,oc sM(V11) l or MsR (V111) F i or M 5 (1X) R Ha1 1 I) or x1) In the formulaeII to XI, R to R have the meanings given for the formula 1, R representsalkyl with 1 to 4 carbon atoms, X represents oxygen or sulphur, Halrepresents chlorine, bromine, or iodine, and M represents ammonium,alkylammonium with 1 to 4 carbon atoms in the alkyl moiety, or alkalimetal.

In reaction 1 it is sometimes necessary to use catalysts, e.gv potassiumiodide. Reaction 2 is initiated by using ultraviolet light, peroxides,e.g. hydrogen peroxide, or hydroquinone. Reactions 1 to 4 are carriedout at a reaction temperature between O90C, in particular at to 60C, atnormal pressure and in solvents or diluents.

Examples of suitable solvents or diluents are: ethers and etherealcompounds, such as diethyl ether, dipropyl ether, dioxan,tetrahydrofuran; amides, such as N,N-dialkylated carboxylic amides;aliphatic, aromatic, and halogenated hydrocarbons, in particularbenzene,

toluene, xylene, chloroform, chlorobenzene; nitriles, such asacetonitrile; dimethyl sulphoxide, ketones, such as acetone, methylethyl ketone, water. Ethanol is also suitable for processes 3 and 4.

The starting materials of the formulae 11, 1V and V1 can be manufacturedin analogous manner to known methods, e.g. those described in OrganicReactions 11," pages 1 to 48.

The compounds of the formula 1 have a broad biocidal activity spectrumand can be used for combating diverse kinds of plant and animal pests.

The compounds of the formula I possess in particular insecticidal andacaricidal properties and can be used against all development stages,e.g. eggs, larvae, pupae, nymphs, and adults of insects andrepresentatives of the order Acarina, for example against insects of thefamilies: Tetigonidae, Gryllidae, Gryllotalpidae, Blattidae, Peduviidae,Phyrrohocoriae, Cimicidae, Delphacidae, Aphididae, Diaspididae,Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae,Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae,Culcidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae aPulicidae, also Acarida of the families lxodidae, Argasidae,Tetranychidae a Dermanyssidae. The insecticidal and/or acaricidal actioncan be substantially broadened and adapted to suit the particularcircumstances by the addition of other insecticides and/or acaricidcs.

Suitable additives include, for example, the following activesubstances:

ORGANIC PHOSPHORUS COM POUNDS Bis-0,0-diethylphosphoric acid anhydride(TEPP) Dimethyl-( 2,2,2-trichlorol -hydroxyethyl phosphonate(TRICHLORFON) 1 ,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED)2,2-dichlorovinyldimethylphosphate (DICHLORVOS)2-methoxycarbamyl-1-methylvinyldimethylphosphate (MEVINPHOS) Dimethyll-methyl-2-( methylcarbamoyl vinylphosphate cis (MONOCROTOPHOS) 3-(dimethoxyphosphinyloxy )-N,N-dimethyl-ciscrotonamide (DICROTOPHOS)2-chloro-2-diethylcarbamoyll -methylvinyldimethylphosphate(PHOSPHAMIDON) 0,0-diethyl-O(or S)-2-(ethylthio)-ethylthiophosphate(DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (Tl-ll- OMETON)0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)0,0-diethyl-S-2-(ethylthio)ethyldithiophosphate (D1- SULFOTON)0,0-dimethyl-S- 2-( ethylsulphinyl )ethylthiophosphate (OXYDEMETONMETHYL) 0,0-dimethy1-S-( 1 ,Z-dicarbethoxyethyldithiophosphate(MALATHION) 0,0,0,0-tetraethyl-S ,S. -methylene-bisdithiophosphate(ETHION) O-ethyl-S,S-dipropyldithioph0sphate 0,0-dimethy1-S-(N-methyl-N-formylcarbamoylmethyl)-dithiophosphate MOTHION) 0,0-dimethyl-S-(N-methylcarbamoylmethyl dithiophosphate (DIMETHOATE) -tetrahydro-4,7-

l,2,3,4,10,lO-hexachloro-6,7-epoxy-l ,4,4a,5,6,7,8,8a-'

octahydro-exol ,4-endo- ,S-dimethanonaphthalene [DIFLORIN] l,2,3,4,l0,lO-hexachloro-5,7-epoxy-1 ,4,4a,5,6,7,8,8a-

octahydro-endo-endo-S ,S-dimethanonaphthalene [ENDRIN] The compounds ofthe formula I may be used as pure active substance or together withsuitable carriers and- /or additives. Suitable carriers and additivescan be solid or liquid and correspond to the substances conventionallyused in formulation technique such, for example, as solvents,dispersants, wetting agents, adhesives, thickeners, binders and/orfertilisers.

For application, the compounds of the formula I may be processed todusts, emulsion concentrates, granules, dispersions, sprays, tosolutions, or suspensions, in the conventional formulation which iscommonly employed in application technology. Mention may also be made ofcattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may take, and be used in, the following forms:

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules.

Liquid forms:

a. active substances which are dispe'rsible in water:

wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone, attaclay, dolomite, diatomaceous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminum silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground veg etable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula I in an organic solvent and applying theresulting solution to a granulated material, for example attapulgite,SIO- granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the activesubstances of the formula I with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde orothers), whereupon a mild polymerisation is carried out that does notaffect the active substances and in the process of which the granulationis carried out during the gel formation. It is more advantageous toimpregnate finished, porous polymer granules (urea/formaldehyde,polyacrylonitrile, polyester or others) which have a specific surfacearea and a favourable predetermi nable adsorption/desorption ratio, withthe active substances, for example in the form of their solutions (in alow boiling solvent) and to remove the solvent. Polymer granules of thiskind in the form of microgranules having a bulk density of 300 g/literto 600 g/liter can also be manufactured with the aid of atomisers. Thedusting can be carried out from aircraft over extensive areas ofcultures of useful plants.

It is also possible to obtain granules by compacting the carrier withthe active substance and carriers and subsequently comminuting theproduct.

To these mixtures can also be added additives which stabilise the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which, for example, improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives are the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, theiralkali metal and alkaline earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20ethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.wettable powders, pastes and emulsifiable concentrates, are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabilise theactive substance, surface-active substance and anti-foam agents and,optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Suitable carriers are,for example, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulphonated naphthalene and sulphonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, as well as alkali,ammonium and alkaline earth metal salts of lignin sulphonic acid, inaddition, alkylaryl sulphonates, alkali and alkaline earth metal saltsof dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such assalts of sulphated hexadecanols, heptadecanols, octadecanols, and saltsof sulphated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salts of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl am- .monium chloride and fatty acidalkali and alkaline ,;earth metal salts.

l a) 40 parts 01 active substance. Suitable. anti-foam agents areslllcones. 5 pans f gudium sulphomm The active substances are mixed.ground. sieved and P1111 fi f l q lz b p sulphmmi strained with .theadditives cited hcrclnabove. ln such h) I 25 8f sii bst nce, a mannerthat. the size of the SOlld'pfll'UClCS does not parts 0; glclumIIglIIHhSIIJLFXIKZIU h l I parts 0 ampagnec a y roxyet y .exceed 0.02 to0.04 u in wettable powders, and 0.03; cellulose mixwre in pastes. Toproduce emulslfiable concentrates and 1.5 partislofsodium dihutylnaphthalene Sulp onate, pastes. dispersing agents such as those citedabove, or- 10 95 parts of silicic acid gamc solvents, and water areused. Examples of suit- 19.5 parts of Champagne chalk, 28.1 parts ofkaolin. able solvents are. alcohols, benzene, xylene, toluene, c) pamofactive Substance dlmethyl sulphoxlde, and mineral oil fractions which2.5 parts of isoctylphenoXy-polyoxyethylerlev o Q ethanol. boll between120 and 350 C. The solvents must be 1'7 pmsofchampugnechalk/hydroxyethyl practically odourless,'not phytotoxlc, and inert tothe H I cellulose mixture (1:1 active Substances 8.3 parts of Sodiumaluminium silicate,

16.5 parts of kieselguhr. Furthermore, the agents according to theinvention 46 parts of kaolin. 7 d) 10 parts of active substance. can beappl ed in the form of solutions. For this pur 3 puns Ofa mixture ofthesodium Salts of pose the active substances, or several active substancessaturated fatty alcohol sulphates, of the general formula 1, aredissolved in suitable'or- 00 5 Pans of naphthulenesulpmmc 1 formaldehydecondensate, gamc solvents, mixtures of solvents or in water. Ali- 31parts of kaolin, phatic and aromatic hydrocarbons, chlorinatedderivatives thereof, alkyl naphthalenes, and mineral oils, sin- Theactive substances are intimately mixed, in suitgly or in admixture witheach other, can be used a orable mixers, with the additives, the mixturebeing then ganik; solvents, ground in the appropriate mills and rollers.Wettable I The content f ti substance i h above d powders are obtainedwhich can be diluted with water to give suspensions of any desiredconcentration.

se'ribedagents 18. between 0.1 to 95 percent, in which connection it'should be mentioned that, in the case of Emuhifiable Concentrates 'ofapplicatiomit is possible to use concentrations of up application fromaircraft or some other suitable means I The-following substances areused to produce a) a y 7 I to 9 pgrcem or even pure uctwe Substancc 10%and b) a -57: emulslfiable concentrate.

The'active substances of the formula 1 can, for exam- P b q l l asfollows: a) 10 I parts of active substance,

' 3.4 parts of epoxidised vegetable oil.

Dusts 13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkyl- The following substances are used tomanufacture a) zlrylsulphonate calcium salt. a 5 a 2% dust: 3:2; 2:?

. b) 25 parts of active substance.

2.5 pans of epoxidised vegetable oil. a) 5 pans of active Substance I 4010 parts altll ylarylsulphonate/fatty alcohol- 95 parts of talcum f et jf b a y I 5 parts of dimethylformamlde.

) I 1 parts of active substance Q7 s am of X ,lene 1 part of highlydisperse silicic acid p i y 97 parts of talcum.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concen- The active substances are mixedwith the carriers and I tration.

ground.

. Granules Spray The following substances are used to produce 5%. Thefollowing Constituents are used to preparea 5% I granules: Spray 5 partsof active substance. 5 parts of active substance. 1 Pan ofcpichlomhydrim Parts r hl' 94 parts of henzine (boiling limits 160190C). 0.2. parts of cetyl polyglycol ether. 5g 3.50 parts ofpolyethylene glycol, T 91 parts of kaolin (particle size 0.3 0.8 mm).EXAMPLE I The active substance is mixed withepiehlorohydrin Manufacturef th C mpound 0f the formula and dissolved with 6 parts of acetone; thepolyethylene glycol and cetyl polyglycol ether are then added. The 0 C HO 0 thus obtained solution is sprayed on kaolin, and the ac- 2 etonesubsequently evaporated in vacuo. Q

I The following constituents are used for the prepara- 25.4 g ofpotassium O-ethyl-S-methoxyethyldithiophostion ofa) a 40%, b) and c)a25%, and d) a 10% wettaphate and 2 g of potassium iodide are given to mlble powder: of acctonitrile. Then 25.3 g of bromosuccinic acid diethylester are added and the mixture is stirred overnight at room temperatureand subsequently for 6 hours at 50C-60C. After the batch has cooled, thesalts are filtered off with suction, the solution is evaporated invacuo, and the residue is'taken up in methylene chloride. The solutionis washed successively with 50 ml of water, 50 ml of normal sodiumhydroxide solution, and 50 ml of water, and the solvent 'is removed invacuo at 50C bath temperature, to leave as residue the active substanceof the above described formula as a yellow oil with the refractive indexn l.4858. Yield: 26.3 g.

The following compounds are also obtained in analogous manner.

A. Insecticidal Ingest Poison Action Tobacco and potato plants weresprayed with a 0.05% aqueous active substance emulsion (obtained from aemulsifiable concentrate.

After the coating had dried, the tobacco plants were populated withSpoa'optera littoralz's caterpillars in the L stage and Heliothisvirescens caterpillers in the L stage and the potato plants withColorado beetle larvae (Leptinotarsa decemlineam). The test was carriedout at 24C and 60% relative humidity. In the above test, the compoundsaccording to Example I displayed good ingest poison action againstSpouoptera litmralis, Heliot/zis virescerzs and Leptinotarsadecemlineata.

B. Insecticidal Contact Action Rooted bean plants (vicia faba) reared inpots were infected one day before the application with about 200leaf-lice (Aphisfabae) per plant. The application to the leavespopulated with the lice was carried out with a pressure spray using aspray broth in a concentration of I,OOO ppm (manufactured from awettable powder). Evaluation took place 24 hours after the application.In the above test the compounds according to Example l displayed goodcontact action against Aphis fabae.

EXAMPLE 3 Action Against Cliilo Suppressalis Six rice plants at a timeof the variety Caloro were transplanted in plastic pots (diameter at thetop 17 cm) and reared to a height of about cm. Infestation with (71170suppressalis larvae (L,; 3-4 mm in length) took place 2 days after theactive substance had been applied in granule form to the paddy water(rate of application: 8 kg of active substance per hectare). Evaluationof the insecticidal action ensued 10 days after application of thegranules.

In the above test, the compounds according to Example I acted againstChilo suppressalis.

EXAMPLE 4 Action against ticks A. R/u'picephalus bursa Five adult ticksor 50 tick larvae were counted into a test tube and immersed for l to 2minutes in 2 ml of an aqueous emulsion series each containing I00, 10, land 0.1 ppm of test substance. The tube was then sealed with astandardised cotton wool plug and stood on its head so as to enable thecotton wool to absorb the active substance emulsion.

In the case of the adults evaluation took place after 2 weeks, and inthat of the larvae after 2 days. Each test was repeated twice.

B. Boophilus microplus (larvae) Tests were carried out with 20 sensitiveand 20 OP resistant larvae with a dilution series analogous to that usedin Test A. (The resistance refers to the tolerability of diazinon). Inthese tests, the compounds according to Example 1 acted against adultsand larvae of R/zipicephalus bursa and sensitive and OP-resistant larvaeof Boop/zilus microplus.

EXAMPLE 5 Action against spider mites Phaseolus vulgaris (plants) wereoverlaid with an infested piece of leaf from a mass culture ofTetranychus urticae 12 hours before the test for acaricidal action. Themobile stages which had spread over the plants were sprayed with theemulsified test preparations from a chromatography atomiser so that thespray broth did not run off. The number of living and dead larvae,adults and eggs were evaluated after 2 to 7 days under a stereoscopicmicroscope and the result was expressed in percentages. During theinterim, the treated plants were kept in greenhouse compartments at 25C.

In the above test, the compounds according to Example I acted againstadults larvae and eggs of Terran chus urticae.

I claim:

1. An insecticidal or acaricidal composition which contains as activecomponent an insecticidally or acaricidally effective amount of acompound of the formula wherein R represents methyl or ethyl, Rrepresents n-pentyl, sec. pentyl, or methoxyethyl and R and R eachrepresents methoxy, ethoxy, n-propoxy, isopropoxy or n-hexyloxy togetherwith suitable carriers.

2. The composition of claim 1 in which R represents methoxyethyl, and Rand R represent methoxy, ethoxy or isopropoxy.

3. A method of combating insects or Acarids which comprises applyingthereto an insecticidally or acaricidally effective amount of a compoundof the formula wherein R, represents methyl or ethyl, R representsn-pentyl, sec. pentyl or methoxyethyl and R and R each representsmethoxy, ethoxy, n-propoxy. isopro- I ethyl ]-dithiophosphate.

7. The method of claim 5 in which said compound isO-ethyl-S-sec.pentyl-S-[ l,2-bis(ethoxycarbonyl)- ethyl-dithiophosphate.

8. The methodof claim 3 wherein R represents methoxyethyl, and R and Rrepresent methoxy, ethoxy or isopropoxy.

9. The method of claim 8 in which said compound isO-ethyl-S-methoxyethyl-S-[ l ,2-bis( ethoxycarbonyl ethylLdithiophosphate. I

1. AN INSECTICIDAL OR ACARICIDAL COMPOSITION WHICH CONTAINS AS ACTIVECOMPONENT AN INSECTICIDALLY OR ACARICIDALLY EFFECTIVE AMOUNT OF ACOMPOUND OF THE FORMULA
 2. The composition of claim 1 in which R2represents methoxyethyl, and R3 and R4 represent methoxy, ethoxy orisopropoxy.
 3. A method of combating insects or Acarids which comprisesapplying thereto an insecticidally or acaricidally effective amount of acompound of the formula
 4. The method of claim 3 wherein R2 ismethoxyethyl.
 5. The method of claim 3 wherein R3 and R4 are methoxy,ethoxy or isopropoxy.
 6. The method of claim 5 in which said compound isO-ethyl-S-n-pentyl-S-(1,2-bis(methoxycarbonyl)-ethyl)-dithiophosphate.7. The method of claim 5 in which said compound isO-ethyl-S-sec.pentyl-S-(1,2-bis(ethoxycarbonyl)-ethyl)-dithiophosphate.8. The method of claim 3 wherein R2 represents methoxyethyl, and R3 andR4 represent methoxy, ethoxy or isopropoxy.
 9. The method of claim 8 inwhich said compound isO-ethyl-S-methoxyethyl-S-(1,2-bis(ethoxycarbonyl)-ethyl)-dithiophosphate.